CA3012238C - Additive manufacturing system implementing hardener pre-impregnation - Google Patents

Additive manufacturing system implementing hardener pre-impregnation Download PDF

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Publication number
CA3012238C
CA3012238C CA3012238A CA3012238A CA3012238C CA 3012238 C CA3012238 C CA 3012238C CA 3012238 A CA3012238 A CA 3012238A CA 3012238 A CA3012238 A CA 3012238A CA 3012238 C CA3012238 C CA 3012238C
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Canada
Prior art keywords
continuous reinforcement
print head
matrix component
matrix
coating
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CA3012238A
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French (fr)
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CA3012238A1 (en
Inventor
Tyler B. Alvarado
Trevor David Budge
Ryan C. STOCKETT
John Swallow
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CC3D LLC
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CC3D LLC
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30Auxiliary operations or equipment
    • B29C64/307Handling of material to be used in additive manufacturing
    • B29C64/314Preparation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0407Processes of polymerisation
    • C08F299/0421Polymerisation initiated by wave energy or particle radiation
    • C08F299/0428Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10Formation of a green body
    • B22F10/18Formation of a green body by mixing binder with metal in filament form, e.g. fused filament fabrication [FFF]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30Process control
    • B22F10/34Process control of powder characteristics, e.g. density, oxidation or flowability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/50Means for feeding of material, e.g. heads
    • B22F12/53Nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10Coating or impregnating independently of the moulding or shaping step
    • B29B15/12Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C31/00Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
    • B29C31/04Feeding of the material to be moulded, e.g. into a mould cavity
    • B29C31/042Feeding of the material to be moulded, e.g. into a mould cavity using dispensing heads, e.g. extruders, placed over or apart from the moulds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C31/00Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
    • B29C31/04Feeding of the material to be moulded, e.g. into a mould cavity
    • B29C31/042Feeding of the material to be moulded, e.g. into a mould cavity using dispensing heads, e.g. extruders, placed over or apart from the moulds
    • B29C31/044Feeding of the material to be moulded, e.g. into a mould cavity using dispensing heads, e.g. extruders, placed over or apart from the moulds with moving heads for distributing liquid or viscous material into the moulds
    • B29C31/045Feeding of the material to be moulded, e.g. into a mould cavity using dispensing heads, e.g. extruders, placed over or apart from the moulds with moving heads for distributing liquid or viscous material into the moulds moving along predetermined circuits or distributing the material according to predetermined patterns
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C31/00Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
    • B29C31/04Feeding of the material to be moulded, e.g. into a mould cavity
    • B29C31/042Feeding of the material to be moulded, e.g. into a mould cavity using dispensing heads, e.g. extruders, placed over or apart from the moulds
    • B29C31/048Feeding of the material to be moulded, e.g. into a mould cavity using dispensing heads, e.g. extruders, placed over or apart from the moulds the material being severed at the dispensing head exit, e.g. as ring, drop or gob, and transported immediately into the mould, e.g. by gravity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154Coating solid articles, i.e. non-hollow articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/165Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
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    • B29C64/205Means for applying layers
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B33Y40/00Auxiliary operations or equipment, e.g. for material handling
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Automation & Control Theory (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Robotics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Toxicology (AREA)
  • Moulding By Coating Moulds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A method is disclosed for additively manufacturing a composite structure. The method may include directing a continuous reinforcement into a print head, and coating the continuous reinforcement with a first matrix component inside of the print head. The method may further include coating the continuous reinforcement with a second matrix component, discharging the continuous reinforcement through a nozzle of the print head, and moving the print head in multiple dimensions during the discharging. The first and second matrix components interact to cause hardening of a matrix around the continuous reinforcement.

Description

ADDITIVE MANUFACTURING SYSTEM IMPLEMENTING
HARDENER PRE-IMPREGNATION
Technical Field [0001] The present disclosure relates generally to a manufacturing system and, more particularly, to an additive manufacturing system implementing hardener pre-impregnation.
Background
[0002] Traditional additive manufacturing is a process of creating three-dimensional parts by depositing overlapping layers of material under the guided control of a computer. A common form of additive manufacturing is known as fused deposition modeling (FDM). Using FDM, a thermoplastic is passed through and liquified within a heated print head. The print head is moved in a predefined trajectory (a.k.a., a tool path) as the material discharges from the print head, such that the material is laid down in a particular pattern and shape of overlapping 2-dimensional layers. The material, after exiting the print head, cools and hardens into a final form. A
strength of the final form is primarily due to properties of the particular thermoplastic supplied to the print head and a 3-dimensional shape formed by the stack of 2-dimensional layers.
[0003] A recently developed improvement over traditional FDM manufacturing involves the use of continuous fibers embedded within material discharging from the print head (a.k.a., Continuous Fiber 3D Printing ¨ CF3DTm). In particular, a matrix is supplied to the print head and discharged (e.g., extruded and/or pultruded) along with one or more continuous fibers also passing through the same head at the same time. The matrix can be a traditional thermoplastic, a powdered metal, a liquid matrix (e.g., a UV curable and/or two-part resin), or a combination of any of these and other known matrixes. Upon exiting the print head, a cure enhancer (e.g., a UV
light, an ultrasonic emitter, a heat source, a catalyst supply, etc.) is activated to initiate and/or complete curing of the matrix. This curing occurs almost immediately, allowing for unsupported structures to be fabricated in free space. And when fibers, particularly continuous fibers, are embedded within the structure, a strength of the structure may be multiplied beyond the matrix-dependent strength. An example of this technology is disclosed in U.S. Patent 9,511,543 that issued to Tyler on December 6, 2016 ("the '543 patent").

100041 In some applications involving opaque fibers (e.g., carbon fibers), high-density fibers, high-concentrations of fibers, large-diameter fibers, etc., it can be difficult for the matrix material located at a center of the corresponding fiber bundle to receive sufficient cure enhancement (e.g., sufficient cure energy, catalyst, etc.). If unaccounted for, the resulting structure may lack strength and/or sag undesirably.
10005] The disclosed system is directed to addressing one or more of the problems set forth above and/or other problems of the prior art.
Summary 10006] In one aspect, the present disclosure is directed to a method of additively manufacturing a composite structure. The method may include directing a continuous reinforcement into a print head, and coating the continuous reinforcement with a first matrix component inside of the print head. The method may further include coating the continuous reinforcement with a second matrix component, discharging the continuous reinforcement through a nozzle of the print head, and moving the print head in multiple dimensions during the discharging. The first and second matrix components interact to cause hardening of a matrix around the continuous reinforcement.
10007] In another aspect, the present disclosure is directed to a system for additively manufacturing a composite structure. The system may include a support, and a print head connected to an end of the support. The print head may have a body with a chamber, in which a continuous reinforcement is coated with one of a resin and a catalyst. The print head may also include a nozzle connected to a discharge end of the body and configured to discharge the continuous reinforcement coated in both the resin and the catalyst. The system may further include a controller in communication with the support and the head. The controller may be configured to selectively cause the support to move the head in multiple dimensions during discharge of the continuous reinforcement from the nozzle, according to specifications for the composite structure.
[0008] In yet another aspect, the present disclosure is directed to a prepreg material for use in additively manufacturing a composite structure. The prepreg material may include a continuous reinforcement, and a catalyst of a multi-part matrix. The multi-part matrix, which also includes at least a resin, is curable around the continuous reinforcement to form the composite structure. The reinforcement is at least partially saturated with the catalyst and substantially free of the resin prior to manufacture of the composite structure, and the reinforcement makes up about 35-70% of the composite structure. The catalyst makes up about .1-10% of the composite structure.
[0008a] According to another embodiment, there is provided a method of additively manufacturing a composite structure, comprising: directing a continuous reinforcement into a print head; coating the continuous reinforcement with a first matrix component inside of the print head; coating the continuous reinforcement with a second matrix component that is different from the first matrix component;
discharging the continuous reinforcement through a nozzle of the print head; and moving the print head in multiple dimensions during the discharging; wherein: the first and second matrix components interact to cause hardening of a matrix around the continuous reinforcement; the first matrix component is a resin, and the second matrix component is one of a catalyst, a hardener, and an initiator; and coating the continuous reinforcement with the second matrix component includes coating the continuous reinforcement with the second matrix component before the continuous reinforcement has been coated with the first matrix component.
[0008b] According to another embodiment, there is provided a method of additively manufacturing a composite structure, comprising: directing a continuous reinforcement that has been coated with a catalyst into a print head; coating the continuous reinforcement with a resin that is different from the catalyst inside of the print head; discharging the continuous reinforcement through a nozzle of the print head; and moving the print head in multiple dimensions during the discharging.
[0008c] According to another embodiment, there is provided a method of additively manufacturing a composite structure, comprising: directing a continuous reinforcement through a catalyst bath inside a print head;
directing the continuous reinforcement through a resin bath inside of the print head; discharging the continuous reinforcement through a nozzle of the print head; and moving the print head in multiple dimensions during the discharging.
Brief Description of the Drawings [0009] Fig. 1 is a diagrammatic illustration of an exemplary disclosed manufacturing system; and [0010] Figs. 2-4 are diagrammatic illustrations an exemplary disclosed heads that may be used in conjunction with the manufacturing system of Fig. 1.
Detailed Description [0011] Fig. 1 illustrates an exemplary system 10, which may be used to continuously manufacture a composite structure 12 having any desired cross-sectional shape (e.g., circular, polygonal, etc.). System 10 may include at least a support 14 and a head 16. Head 16 may have a body 18 that is coupled to and moved by support 14, and a nozzle 20 located at an opposing discharge end of body 18.
In the disclosed embodiment of Fig. 1, support 14 is a robotic arm capable of moving head 16 in multiple directions during fabrication of structure 12, such that a resulting longitudinal axis of structure 12 is three-dimensional. It is contemplated, however, that support 14 could alternatively be an overhead gantry or a hybrid gantry/arm also capable of moving head 16 in multiple directions during fabrication of structure 12. Although support 14 is shown as being capable of 6-axis movements, it is contemplated that any other type of support 14 capable of moving head 16 in the same or in a different manner could also be utilized, if desired. In some embodiments, a drive may mechanically couple head 16 to support 14, and may include components that cooperate to move and/or supply power or materials to head 16.
10012] Body 18 may be configured to receive or otherwise contain a matrix material. The matrix material may include any type of matrix material (e.g., a liquid resin, such as a zero volatile organic compound resin; a powdered metal; etc.) that is curable. Exemplary resins include thermosets, single- or multi-part epoxy resins, polyester resins, cationic epoxies, acrylated epoxies, urethanes, esters, thermoplastics, photopolymers, polyepoxides, thiols, alkenes, thiol-enes, and more. In one embodiment, the matrix material inside body 18 may be pressurized, for example by an external device (e.g., an extruder or another type of pump - not shown) that is fluidly connected to head 16 via a corresponding conduit (not shown). In another embodiment, however, the pressure may be generated completely inside of body 18 by a similar type of device. In yet other embodiments, the matrix material may be gravity-fed through and/or mixed within body 18. In some instances, the matrix material inside body 18 may need to be kept cool and/or dark to inhibit premature curing;
while in other instances, the matrix material may need to be kept warm for the same reason. In either situation, body 18 may be specially configured (e.g., insulated, chilled, and/or warned) to provide for these needs.
[0013] The matrix material may be used to coat, encase, or otherwise surround any number of continuous reinforcements (e.g., separate fibers, tows, rovings, and/or sheets of material) and, together with the reinforcements, make up at least a portion (e.g., a wall) of composite structure 12.
The reinforcements may be stored within (e.g., on separate internal spools -not shown) or otherwise passed through body 18 (e.g., fed from external spools 21 ¨ See Figs. 2-4).
When multiple reinforcements are simultaneously used, the reinforcements may be of the same type and have the same diameter and cross-sectional shape (e.g., circular, square, flat, etc.), or of a different type with different diameters and/or cross-sectional shapes. The reinforcements may include, for example, carbon fibers, vegetable fibers, wood fibers, mineral fibers, glass fibers, metallic wires, optical tubes, etc. It should be noted that the term "reinforcement" is meant to encompass both structural and non-structural types of continuous materials that can be at least partially encased in the matrix material discharging from nozzle 20.
[0014] The reinforcements may be exposed to (e.g., coated with) the matrix material while the reinforcements are passing through body 18. The matrix material, dry reinforcements, and/or reinforcements that are already exposed to the matrix material (e.g., wetted reinforcements) may be transported into body 18 in any manner apparent to one skilled in the art.
[0015] The matrix material and reinforcement may be discharged from nozzle 20 via at least two different modes of operation. In a first mode of operation, the matrix material and reinforcement are extruded (e.g., pushed under pressure and/or mechanical force) from nozzle 20, as head 16 is moved by support 14 to create the 3-dimensional shape of structure 12. In a second mode of operation, at least the reinforcement is pulled from nozzle 20, such that a tensile stress is created in the reinforcement during discharge. In this mode of operation, the matrix material may cling to the reinforcement and thereby also be pulled from nozzle 20 along with the reinforcement, and/or the matrix material may be discharged from nozzle 20 under pressure along with the pulled reinforcement. In the second mode of operation, where the matrix material is being pulled from nozzle 20, the resulting tension in the reinforcement may increase a strength of structure 12, while also allowing for a greater length of unsupported material to have a straighter trajectory (i.e., the tension may act against the force of gravity to provide free-standing support for structure 12).
[0016] The reinforcement may be pulled from nozzle 20 as a result of head 16 moving away from an anchor point 22. In particular, at the start of structure-formation, a length of matrix-impregnated reinforcement may be pulled and/or pushed from nozzle 20, deposited onto anchor point 22, and cured, such that the discharged material adheres to anchor point 22.
Thereafter, head 16 may be moved away from anchor point 22, and the relative movement may cause the reinforcement to be pulled from nozzle 20. It should be noted that the movement of reinforcement through body 18 could be assisted (e.g., via one or more internal and/or external feed mechanisms ¨ not shown), if desired. However, the discharge rate of reinforcement from nozzle 20 may primarily be the result of relative movement between head 16 and anchor point 22, such that tension is created and maintained within the reinforcement. It is contemplated that anchor point 22 could be moved away from head 16 instead of or in addition to head 16 being moved away from anchor point 22.
[0017] One or more cure enhancers (e.g., a UV light, an ultrasonic emitter, a laser, a heater, a catalyst dispenser, etc.) 24 may be mounted proximate (e.g., within, on, and/or trailing from) head 16 (e.g., at a base of body 18, inside of body 18, outside of body 18, or otherwise adjacent nozzle 20) and configured to enhance a cure rate and/or quality of the matrix material as it is discharged from head 16. Cure enhancer 24 may be controlled to selectively expose internal and/or external surfaces of structure 12 to energy (e.g., UV light, electromagnetic radiation, vibrations, heat, a chemical catalyst, hardener, or initiator, etc.) during the formation of structure 12.
The energy may increase a rate of chemical reaction occurring within the matrix material, sinter the material, harden the material, or otherwise cause the material to cure as it discharges from head 16.
[0018] A controller 26 may be provided and communicatively coupled with support 14, head 16, and any number and type of cure enhancers 24. Controller 26 may embody a single processor or multiple processors that include a means for controlling an operation of system(s) 10 and/or 12.
Controller 26 may include one or more general- or special-purpose processors or microprocessors.
Controller 26 may further include or be associated with a memory for storing data such as, for example, design limits, performance characteristics, operational instructions, matrix characteristics, reinforcement characteristics, characteristics of structure 12, and corresponding parameters of each component of system 10. Various other known circuits may be associated with controller 26, including power supply circuitry, signal-conditioning circuitry, solenoid/motor driver circuitry, communication circuitry, and other appropriate circuitry. Moreover, controller 26 may be capable of communicating with other components of system 10 via wired and/or wireless transmission.
[0019] One or more maps may be stored in the memory of controller 26 and used during fabrication of structure 12. Each of these maps may include a collection of data in the form of lookup tables, graphs, and/or equations. In the disclosed embodiment, the maps are used by controller 26 to determine desired characteristics of cure enhancers 24, the associated matrix, and/or the associated reinforcements at different locations within structure 12. The characteristics may include, among others, a type, quantity, and/or configuration of reinforcement and/or matrix to be discharged at a particular location within structure 12, and/or an amount, shape, and/or location of desired curing. Controller 26 may then correlate operation of support 14 (e.g., the location and/or orientation of head 16) and/or the discharge of material from nozzle 20 (a type of material, desired performance of the material, cross-linking requirements of the material, a discharge rate, etc.) with the operation of cure enhancers 24 such that structure 12 is produced in a desired manner.
[0020] In some applications, care must be taken to ensure that each of the fibers passing through head 16 are sufficiently coated with matrix material (i.e., coated sufficient to ensure proper bonding and curing) prior to discharge from nozzle 20. As shown in Fig. 2, the fibers may be exposed to the matrix material during travel through one or more chambers 28 that are located inside of body 18.
[0021] In the embodiment of Fig. 2, the matrix material being applied to the reinforcement inside of head 16 is a multi-part matrix. In particular, the matrix includes a first matrix component (e.g., an epoxy resin, a polyester resin, a vinylester resin, or another type of resin) and at least a second matrix component (e.g., a hardener, a catalyst, or another initiator) that, under controlled conditions, together react or causes a reaction to form a cured and hardened matrix encasing the associated reinforcements. At least two separate chambers 28 are located inside of body 18 of Fig. 2, for separately coating the reinforcements with the first and second matrix components. These chambers 28 include a first chamber 28a that is sequentially arranged with a second chamber 28b. in relation to a travel direction of the reinforcement(s) through head 16 (e.g., from spool 21 to nozzle 20). In this example, first chamber 28a contains one of the first and second matrix components, while second chamber 28b contains the other of the first and second matrix components. It should be noted that both sequential orders of the first and second matrix components within body 18 are contemplated in this disclosure.
[0022] The first and/or second matrix components may be supplied to the corresponding chamber(s) 28a, 28b in several different ways. For example, one or both of the first and second matrix components may be provided as a gas-, a liquid-, or a powder-stream via a jet 30 (see Fig. 4);
as a liquid bath via a supply inlet 32 or jet 30; as a suspended powder via a pressurized conduit 34, supply inlet 32, or jet 30; or in another manner known in the art. In some embodiments, a regulating device 36 (e.g., opposing rollers, a squeegee, a wiper, a brush, an air jet, etc.) may be disposed between first and second chambers 28a and 28b (and/or downstream of second chamber 28b) to remove excess matrix component from the reinforcements prior to the coated reinforcements entering second chamber 28b (and/or just prior to the coated reinforcement entering nozzle 20). In this way, mixing of any excess matrix component clinging to the reinforcements, with the subsequent supply of matrix component inside of second chamber 28b (and corresponding premature curing of the mixture inside of second chamber 28b), may be inhibited. In some applications, a mechanical means (e.g., a tube surrounding the catalyst-coated reinforcement and extending to jet(s) 30) may be used to inhibit premature mixing of the catalyst with the base matrix. In other embodiments, curing of the matrix components may primarily initiate or proceed rapidly only when a temperature of the matrix components exceeds a minimum threshold. regardless of undesired mixing inside second chamber 28b. In these embodiments, body 18 of head 16 may be maintained below the minimum threshold, to inhibit premature curing.
100231 It should be noted that, while a single jet 30 is shown as being oriented generally orthogonal to an axis of the reinforcement passing through head 16, it is contemplated that any number of jets 30 could be utilized and oriented at a different angle, if desired. For example, jet(s) 30 could be tilted downward toward nozzle 20 and at an oblique angle relative to the axis of the reinforcement. This may help to reduce splashing and contamination of catalyst within matrix reservoir 28, in some applications. In addition, it is contemplated that a purge fluid (e.g., mineral oil) could be periodically (e.g., at a start and/or end of a fabrication event) passed through jet(s) 30, if desired.
100241 As the reinforcements pass through first and second chambers 28a, 28b, the reinforcements may be coated with overlapping inner and outer layers of the first and second matrix components. In some embodiments, the layers remain substantially separated until the reinforcements reach nozzle 20. In other embodiments, some mixing of the first and second matrix components at their corresponding boundaries occurs, prior to the reinforcements reaching nozzle 20. Regardless of how much mixing occurs upstream of nozzle 20, the mechanical motion of the coated reinforcements converging and being discharged through nozzle 20 may enhance mixing of the first and second matrix components. And upon exiting nozzle 20, curing may begin or speed up as both a result of the increased mixing and exposure to energy from cure enhancers 24. It is contemplated that, in some applications, cure enhancers 24 may be unnecessary, as the mixing of the two matrix components (and/or exposure of the mixed components to ambient conditions) at nozzle 20 may be sufficient for complete curing. It is further contemplated that nozzle 20 (e.g., a tip end of nozzle 20) could be energized (e.g., heated, vibrated, etc.) to increase a rate of cure, if desired.
100251 In some embodiments, in addition to the two matrix components described above, an additive or third matrix component may be mixed into one or both of the first and second matrix components. The additive may include, for example, a filler and/or an additional or different catalyst. For instance, a UV cure initiator (e.g., different from the second matrix component) could be mixed into the first matrix component, if desired. The UV cure initiator may be sufficient to raise a temperature of the matrix mixture coating the reinforcements to the minimum threshold temperature discussed above, upon exposure to light energy from cure enhancers 24. Thereafter, the second matrix matrix component in the mixture coating the reinforcements may be triggered to cause full and complete curing of the first matrix component in the mixture.
[0026] In some situations, the reinforcements being fed into head 16 may include many (e.g., thousands) of individual fibers that are bound, woven, twisted or otherwise gathered together. In these situations, it can be difficult to ensure that a sufficient amount of the first and/or second matrix components coats each of the individual fibers. This may be even more difficult when large tows or thick ribbons of fibers are passed through head 16 at high speeds. For this reason, head 16 may be equipped with one or more fiber-teasing mechanisms 38 that help to separate and/or flatten the tows or ribbons, such that the matrix components can penetrate to the centermost fibers more thoroughly and/or quicker. Mechanisms 38 may be located inside and/or outside of body 18, at a position upstream of and/or between chamber(s) 28. Mechanisms 38 may include, for example, brushes, a tortuous path of protrusions (e.g., rollers, fingers, or stationary bumps), air and/or resin jets, and other similar devices.
[0027] Fig. 3 illustrates an alternative embodiment of head 16 that is also configured to discharge reinforcements coated in a multi-part matrix. In this embodiment, however, body 18 includes a single chamber 28. The single chamber 28 may hold either the first matrix component or the second matrix component discussed above, with or without the additive. The remaining matrix component may already coat the reinforcement and be supplied to head 16 as a prepreg material (e.g., from spool 21 and/or from an upstream and offboard coating chamber ¨ not shown). In other words, head 16 may be configured to apply only part of the multi-part matrix, with the remaining part(s) already being applied to the reinforcements at an earlier time and/or upstream location. In this embodiment, care should be taken to ensure that the prepreg material is kept at conditions that extend life of the material prior to the material being fed into head 16, for example, in dry, cool, and/or dark conditions.
[0028] Fig. 4 illustrates another embodiment having a single-chamber head 16, which is also configured to discharge reinforcements coated in a multi-part matrix. Like the embodiment of Fig.
3, the single chamber 28 of Fig. 4 may hold either the first matrix component or the second matrix component discussed above (with or without the additive). The remaining matrix component may be injected, sprayed, or otherwise advanced (e.g., via jet 30, inlet 32, and/or conduit 34) into head 16 at a discharge end. In one example, the remaining matrix component is advanced into body 18 at a discharge end of chamber 28, just upstream of nozzle 20. In another embodiment, the remaining matrix component is advanced directly into nozzle 20. The location of the matrix component advancement should be far enough upstream of the tip end of nozzle 20 to ensure adequate mixing of the matrix components, yet downstream enough to inhibit premature curing inside of nozzle 20. It is contemplated that the reinforcements fed into head 16, in the embodiment of Fig. 4, may include dry fibers or fibers pre-impregnated with another material (e.g., the additive), if desired.
[0029] Regardless of the particular embodiment (e.g., the embodiment of Fig.
2, Fig. 3, or Fig. 4) utilized to fabricate structure 12, structure 12 may be comprised of at least three primary constituents. As described above, these constituents may include the reinforcement (e.g., the continuous fibers, tows, ribbons, sheets, etc.), the first matrix component (e.g., the resin, such as an epoxy resin), and the second matrix component (e.g., the hardener, catalyst, initiator, etc.). And in some embodiments, the additive (e.g., the UV cure initiator) may be mixed into the first and/or second matrix components at any desired point in the manufacturing process.
For the purposes of this disclosure, the reinforcement may comprise about (e.g., within engineering tolerances) 35-70%
(e.g., by weight and/or volume) of structure 12; the first matrix component may comprise about 30-50% of structure 12, and the second matrix component may comprise about .1-10%
of structure 12.
In embodiments including the additive, the additive may comprise about 0-10%.
Industrial Applicability [0030] The disclosed system may be used to continuously manufacture composite structures having any desired cross-sectional shape, length, density, and/or strength.
The composite structures may include any number of different reinforcements of the same or different types, diameters, shapes, configurations, and consists, and/or any number of different matrixes.
Operation of system will now be described in detail.
[0031] At a start of a manufacturing event, information regarding a desired structure 12 may be loaded into system 10 (e.g., into controller 26 that is responsible for regulating operation of support 14, cure enhancer(s) 24, jet(s) 30, regulating device(s) 36, fiber-teasing mechanism(s) 38, and/or any other associated components). This information may include, among other things, a size (e.g., diameter, wall thickness, length, etc.), a contour (e.g., a trajectory), surface features (e.g., ridge size, location, thickness, length; flange size, location, thickness, length; etc.), connection geometry (e.g., locations and sizes of couplings, tees, splices, etc.), location-specific matrix stipulations, location-specific reinforcement stipulations, desired cure rates, cure locations, cure shapes, cure amounts, etc.

It should be noted that this information may alternatively or additionally be loaded into system 10 at different times and/or continuously during the manufacturing event, if desired.
[0032] Based on the component information, a specific nozzle 20 and/or cure enhancer configuration may be connected to head 16 (e.g., to the discharge end of body 18), and one or more different (e.g., different sizes, shapes, and/or types of) reinforcements and/or matrix materials may be selectively installed within system 10 and/or continuously supplied into nozzle 20. The corresponding reinforcements (e.g., prepreg or dry fibers, tows, ribbons, or sheets) may be passed through one or more fiber-teasing mechanisms 38 (e.g., between the bristles of adjacent brushes, and/or over or around protrusions, etc.) and nozzle 20, and thereafter connected to a pulling machine (not shown) and/or to a mounting fixture (e.g., to anchor point 22).
Installation of the matrix material may include filling chamber(s) 28 and/or coupling of an extruder (not shown) to head 16.
[0033] Head 16 may be moved by support 14 under the regulation of controller 26 to cause matrix-coated reinforcements to be placed against or on a corresponding anchor point 22. Cure enhancers 24 may then be selectively activated (e.g., turned on/off and/or intensity-adjusted by controller 26) to cause hardening of the matrix material surrounding the reinforcements, thereby bonding the reinforcements to anchor point 22.
[0034] The component information may then be used to control operation of system 10. For example, the reinforcements may be pulled through fiber-teasing mechanism(s) 38; separated and/or flattened; submerged within the first matrix component, wrung out by regulating device 36;
submerged within the second matrix component; and then discharged from nozzle 20. Controller 26 selectively cause support 14 to move head 16 in a desired manner at this time, such that an axis of the resulting structure 12 follows a desired trajectory (e.g., a free-space, unsupported, 3-D
trajectory). In addition, cure enhancers 24 may be selectively activated by controller 26 during material discharge to initiate, speed up, or complete hardening of the liquid matrix mixture. Once structure 12 has grown to a desired length, structure 12 may be disconnected (e.g., severed) from head 16 in any desired manner.
[0035] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed systems and head. Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the disclosed systems and heads. It is intended that the specification and examples be considered as exemplary only, with a true scope being indicated by the following claims and their equivalents.

Claims (18)

CLAIMS:
1. A method of additively manufacturing a composite structure, comprising:
directing a continuous reinforcement into a print head;
coating the continuous reinforcement with a first matrix component inside of the print head;
coating the continuous reinforcement with a second matrix component that is different from the first matrix component;
discharging the continuous reinforcement through a nozzle of the print head;
and moving the print head in multiple dimensions during the discharging;
wherein:
the first and second matrix components interact to cause hardening of a matrix around the continuous reinforcement;
the first matrix component is a resin, and the second matrix component is one of a catalyst, a hardener, and an initiator; and coating the continuous reinforcement with the second matrix component includes coating the continuous reinforcement with the second matrix component before the continuous reinforcement has been coated with the first matrix component.
2. The method of claim 1, wherein coating the continuous reinforcement with the second matrix component includes coating the continuous reinforcement inside the print head with the second matrix component after the continuous reinforcement has been coated with the first matrix component.
3. The method of claim 2, wherein coating the continuous reinforcement with the second matrix component includes at least one of directing the second matrix component into the print head at a discharge end of a first matrix component chamber or directing the second matrix component into the nozzle.
4. The method of claim 1, wherein coating the continuous reinforcement with the second matrix component includes coating the continuous reinforcement prior to directing the continuous reinforcement into the print head.
5. The method of claim 1, further including exposing a mixture of the first and second matrix components coating the continuous reinforcement to a cure energy after the continuous reinforcement has been discharged from the nozzle.
6. The method of claim 5, wherein the cure energy is UV light.
7. The method of claim 1, further including at least one of separating and flattening the continuous reinforcement prior to coating the continuous reinforcement with at least one of the first and second matrix components.
8. The method of claim 1, wherein coating the continuous reinforcement with the first matrix component includes submerging the continuous reinforcement in a bath of the first matrix component.
9. The method of claim 1, wherein coating the continuous reinforcement with the first matrix component includes exposing the continuous reinforcement to at least one of a gas and a powder of the first matrix component.
10. A method of additively manufacturing a composite structure, comprising:
directing a continuous reinforcement that has been coated with a catalyst into a print head;
coating the continuous reinforcement with a resin that is different from the catalyst inside of the print head;
discharging the continuous reinforcement through a nozzle of the print head;
and moving the print head in multiple dimensions during the discharging.
11. The method of claim 10, further including:

coating the continuous reinforcement with the catalyst; and at least partially curing the catalyst prior to the continuous reinforcement entering the print head.
12. The method of claim 10, further including exposing a mixture of the catalyst and the resin coating the continuous reinforcement to a cure energy after the continuous reinforcement has been discharged from the nozzle.
13. The method of claim 12, wherein the cure energy is UV light.
14. The method of claim 10, wherein coating the continuous reinforcement with the resin includes at least one of submerging the continuous reinforcement in a bath of the resin and spraying resin into the continuous reinforcement.
15. A method of additively manufacturing a composite structure, comprising:
directing a continuous reinforcement through a catalyst bath inside a print head;
directing the continuous reinforcement through a resin bath inside of the print head;
discharging the continuous reinforcement through a nozzle of the print head;
and moving the print head in multiple dimensions during the discharging.
16. The method of claim 15, further including exposing a mixture of the catalyst and the resin coating the continuous reinforcement to a cure energy after the continuous reinforcement has been discharged from the nozzle.
17. The method of claim 16, wherein the cure energy is UV light.
18. The method of claim 15, further including at least one of separating and flattening the continuous reinforcement prior to directing the continuous reinforcement through at least one of the catalyst bath and the resin bath.
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